Method of forming transition metal dichalcogenide thin film

ABSTRACT

A method of forming a transition metal dichalcogenide thin film on a substrate includes treating the substrate with a metal organic material and providing a transition metal precursor and a chalcogen precursor around the substrate to synthesize transition metal dichalcogenide on the substrate. The transition metal precursor may include a transition metal element and the chalcogen precursor may include a chalcogen element.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. application Ser. No.16/928,560, filed Jul. 14, 2020, which claims the benefit of KoreanPatent Application No. 10-2019-0085821, filed on Jul. 16, 2019, in theKorean Intellectual Property Office, the disclosure of each of which isincorporated herein in its entirety by reference.

BACKGROUND 1. Field

The present disclosure relates to a method of forming a transition metaldichalcogenide thin film.

2. Description of Related Art

Transition metal dichalcogenide (TMD) is a two-dimensional materialhaving semiconductor characteristics. Transition metal dichalcogenideincludes two chalcogenide atom layers, each having a two-dimensionalhexagonal honeycomb structure, and one metal atom layer interposedbetween the chalcogenide atom layers. Transition metal dichalcogenide isa material that can be applied to various devices because it hasexcellent electrical properties, its characteristics do not changegreatly even when its thickness decreases to the nanoscale, and it hashigh mobility.

SUMMARY

One or more embodiments provide a method of forming a transition metaldichalcogenide thin film.

According to an embodiment, a method of forming a transition metaldichalcogenide thin film on a substrate is provided. The method includestreating the substrate with a metal organic material and providing atransition metal precursor and a chalcogen precursor around thesubstrate to synthesize a transition metal dichalcogenide on thesubstrate. The transition metal precursor includes a transition metalelement and the chalcogen precursor includes a chalcogen element.

Additional aspects will be set forth in part in the description whichfollows and, in part, will be apparent from the description, or may belearned by practice of the presented embodiments of the disclosure.

In some embodiments, the metal organic material may include a metal forinducing adsorption of the transition metal precursor and the chalcogenprecursor.

In some embodiments, the metal organic material may include at least oneof Al, Ti, and Ni. The metal organic material may include at least oneof trimethylaluminum, tris(demethylamido)aluminum, triisobutylaluminum,titanium isopropoxide, tetrakis(dimethylamido)titanium,bis(cyclopentadienyl)nickel, and bis(ethylcyclopentadienyl)nickel.

In some embodiments, the transition metal dichalcogenide may berepresented by Formula 1 below:M_(1-a)M_(a)′X_(2(1-b))X_(2b)′  <Formula 1>wherein, in Formula 1,

M and M′ may be different transition metal elements from each other,

X and X′ may be different chalcogen elements from each other,

0≤a<1, and

0≤b<1.

In some embodiments, the transition metal element may include at leastone of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Tc, Re, Co, Rh, Ir, Ni, Pd, Pt, Zn,and Sn, and the chalcogen element may include at least one of S, Se, andTe.

In some embodiments, the transition metal precursor may include atransition metal halide.

In some embodiments, the transition metal halide may include at leastone of MoF₃, MoF₆, MoF₄, Mo₄F₂₀, MoCl₂, MoCl₃, MoCl₆, MoCl₄, MoCl₅,MoBr₃, MoBr₄, MoI₂, MoI₃, MoI₄, WF₆, WF₄, [WF₅]₄, WCl₂, WCl₆, WCl₄,[WCl₅]₂, [W₆Cl₁₂]Cl₆, WBr₃, WBr₆, WBr₄, WBr₅, W₆Br₁₄, WI₂, WI₃, WI₄,VF₂, VF₃, VF₄, VF₅, VCl₂, VCl₃, VCl₄, VBr₂, VBr₃, VBr₄, VI₂, VI₃, VI₄,NbCl₃, NbCl₄, NbCl₅, NbBr₄, NbBr₅, NbI₃, NbI₄, NbI₅, TaF₃, [TaF₅]₄,TaCl₃, TaCl₄, TaCl₅, TaBr₃, TaBr₄, TaBr₅, TaI₄, TaI₅, TiF₂, TiF₃, TiF₄,TiCl₄, TiCl₃, TiCl₂, TiBr₃, TiBr₄, HfCl₄, HfBr₂, HfBr₄, HfI₃, HfI₄,ZrF₄, ZrCl₂, ZrCl₃, ZrCl₄, ZrBr₃, ZrBr₄, ZrI₂, ZrI₃, ZrI₄, TcF₆, TcF₅,TcCl₄, TcCl₆, TcBr₄, ReF₆, ReF₄, ReF₅, ReF₇, Re₃Cl₉, ReCl₅, ReCl₄,ReCl₆, ReBr₃, ReBr₄, ReBr₅, ReI₃, ReI₄, CoF₂, CoF₃, CoF₄, CoCl₂, CoCl₃,CoBr₂, CoI₂, RhF₃, RhF₆, RhF₄, [RhF₅]₄, RhCl₃, RhBr₃, RhI₃, IrF₃, IrF₆,IrF₄, [IrF₅]₄, IrCl₂, IrCl₃, IrCl₄, IrBr₂, IrBr₃, IrBr₄, IrI₂, IrI₃,IrI₄, NiF₂, NiCl₂, NiBr₂, NiI₂, PdF₂, PdF₄, PdCl₂, PdBr₂, PdI₂, PtF₆,PtF₄, [PtF₅]₄, PtCl₂, PtCl₃, PtCl₄, Pt₆Cl₁₂, PtBr₂, PtBr₃, PtBr₄, PtI₂,PtI₃, PtI₄, GaF₃, GaCl₂, GaCl₃, GaBr₃, GaI₃, SnF₂, SnF₄, SnCl₂, SnCl₄,SnBr₂, SnBr₄, SnI₂, and SnI₄.

In some embodiments, the chalcogen precursor may include at least one ofsulfur, hydrogen sulfide (H₂S), diethyl sulfide, dimethyl disulfide,ethyl methyl sulfide, (Et₃Si)₂S, selenium vapor, hydrogen selenide(H₂Se), diethyl selenide, dimethyl diselenide, ethyl methyl selenide,(Et₃Si)₂Se, selenium vapor, tellurium vapor, hydrogen telluride (H₂Te),dimethyl telluride, diethyl telluride, ethyl methyl telluride, and(Et₃Si)₂Te.

In some embodiments, the substrate may include at least one of silicon,silicon oxide, aluminum oxide, magnesium oxide, silicon carbide, siliconnitride, glass, quartz, sapphire, graphite, graphene, polyimidecopolymer, polyimide, polyethylene naphthalate (PEN), a fluoropolymer(FEP), and polyethylene terephthalate (PET).

In some embodiments, the treating the substrate with the metal organicmaterial may include: providing the metal organic material around thesubstrate; and heat-treating a vicinity of the substrate to decomposethe metal organic material.

In some embodiments, the heat-treating the vicinity of the substrateproduces a metal by the decomposition of the metal organic material onthe substrate. The heat-treating the vicinity of the substrate may beperformed at 300° C. to 500° C.

In some embodiments, the providing the transition metal precursor andthe chalcogen precursor around the substrates may form the transitionmetal dichalcogenide thin film by an atomic layer deposition (ALD)process or a chemical vapor deposition (CVD) process.

In some embodiments, the treating the substrate with the metal organicmaterial may be performed before the providing the transition metalprecursor and the chalcogen precursor around the substrate to synthesizethe transition metal dichalcogenide or during the providing thetransition metal precursor and the chalcogen precursor around thesubstrate to synthesize the transition metal dichalcogenide.

In some embodiments, the transition metal precursor and the chalcogenprecursor may be provided simultaneously to the substrate or alternatelyprovided to the substrate.

According to another embodiment, a method of forming a transition metaldichalcogenide thin film on a substrate is provided. The method includestreating the substrate with a metal organic material and synthesizingtransition metal dichalcogenide on the substrate using an atomic layerdeposition (ALD) process.

In some embodiments, the forming the transition metal dichalcogenidethin film may be performed at 300° C. to 500° C.

According to another embodiment, a method of forming a transition metaldichalcogenide thin film on a substrate is provided. The method includestreating the substrate with a metal organic material and synthesizing atransition metal dichalcogenide on the substrate using a chemical vapordeposition (CVD) process.

In some embodiments, the forming the transition metal dichalcogenidethin film may be performed at 300° C. to 500° C.

According to another embodiment, a method of forming a transition metaldichalcogenide thin film on a substrate is provided. The method mayinclude treating a substrate to provide a metal on a surface of thesubstrate and depositing a transition metal dichalcogenide layer on thesurface of the substrate. The metal may include at least one of Al, Ti,and Ni. The treating the substrate and the depositing the transitionmetal dichalcogenide may be performed at process chamber temperatures ina range of 300° C. to 500° C.

In some embodiments, the depositing the transition metal dichalcogenidelayer may be an atomic layer deposition (ALD) process or a chemicalvapor deposition (CVD) process.

In some embodiments, the substrate may include at least one of silicon,silicon oxide, aluminum oxide, magnesium oxide, silicon carbide, siliconnitride, glass, quartz, sapphire, graphite, graphene, polyimidecopolymer, polyimide, polyethylene naphthalate (PEN), a fluoropolymer(FEP), and polyethylene terephthalate (PET).

In some embodiments, the treating the substrate may be performed beforethe depositing the transition metal dichalcogenide layer.

In some embodiments, the treating the substrate is performed during thedepositing the transition metal dichalcogenide layer.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other aspects, features, and advantages of certainembodiments of the disclosure will be more apparent from the followingdescription taken in conjunction with the accompanying drawings, inwhich:

FIG. 1 is a flowchart illustrating a method of forming a transitionmetal dichalcogenide thin film, according to an example embodiment;

FIG. 2 is a flowchart illustrating a method of forming a transitionmetal dichalcogenide thin film, according to another example embodiment;

FIGS. 3A and 3B are a Raman spectrum and a PL spectrum illustrating acase where an MoS₂ thin film is deposited on an SiO₂ substrate using anALD process without surface-treating the SiO₂ substrate usingtrimethylaluminum (TMA);

FIGS. 4A and 4B are a Raman spectrum and a PL spectrum illustrating acase where an MoS₂ thin film was deposited after surface-treating a SiO₂substrate for 20 cycles using trimethylaluminum (TMA) through an ALDprocess;

FIGS. 5A and 5B are a Raman spectrum and a PL spectrum illustrating acase where an MoS₂ thin film was deposited through an ALD process aftersurface-treating a SiO₂ substrate for 50 cycles using trimethylaluminum(TMA) through the ALD process; and

FIG. 6 is a flowchart illustrating a method of forming a transitionmetal dichalcogenide thin film, according to another example embodiment.

DETAILED DESCRIPTION

Reference will now be made in detail to embodiments, examples of whichare illustrated in the accompanying drawings, wherein like referencenumerals refer to like elements throughout. In this regard, the presentembodiments may have different forms and should not be construed asbeing limited to the descriptions set forth herein. Accordingly, theembodiments are merely described below, by referring to the figures, toexplain aspects. As used herein, the term “and/or” includes any and allcombinations of one or more of the associated listed items.

Expressions such as “at least one of,” when preceding a list ofelements, modify the entire list of elements and do not modify theindividual elements of the list.

Hereinafter, when a layer, film, region, plate, or the like is referredto as being “on” or “on” another portion throughout the specification,this includes not only the case directly above another portion but alsothe case where there is another portion in between. As used herein, thesingular forms “a,” “an” and “the” are intended to include the pluralforms as well, unless the context clearly indicates otherwise. the terms“comprise”, “include”, “have”, etc. when used in this specification,specify the presence of stated features, integers, steps, operations,elements, components, and/or combinations of them but do not precludethe presence or addition of one or more other features, integers, steps,operations, elements, components, and/or combinations thereof.

The use of the term “the above” and similar terminology may be used inthe singular forms and the plural forms. If steps constituting themethod are not explicitly stated or contrary to the steps, the steps maybe performed in a suitable order. It is not necessarily limited to theorder of description of the above steps. The use of all examples orexemplary terms is merely for the purpose of describing technicalconcepts in detail and is not limited in scope by the examples orexemplary terms unless defined by the claims.

Transition metal dichalcogenide (TMD) includes two chalcogenide atomlayers each having a two-dimensional hexagonal honeycomb structure, andone metal atom layer interposed between the chalcogenide atom layers.The transition metal dichalcogenide may be represented by Formula 1below.M_(1-a)M_(a)′X_(2(1-b))X_(2b)′  <Formula 1>

Here, M and M′ are different transition metal elements from each other,X and X′ are different chalcogen elements from each other, and 0≤a<1 and0≤b<1 are satisfied.

The transition metal element may include at least one (and/or at leasttwo) selected from Ti, Zr, Hf, V, Nb, Ta, Mo, W, Tc, Re, Co, Rh, Ir, Ni,Pd, Pt, Zn, and Sn. Further, the chalcogen element may include at leastone (and/or at least two) selected from S, Se, and Te. However,inventive concepts are not limited thereto.

In the following embodiments, methods of forming a transition metaldichalcogenide thin film on a substrate will be described.

FIG. 1 is a flowchart illustrating a method of forming a transitionmetal dichalcogenide thin film, according to an example embodiment.

Referring to FIG. 1 , first, a substrate, on which a transition metaldichalcogenide thin film is to be formed, is prepared (110). Here, thesubstrate may include various materials. For example, the substrate mayinclude a metal, a semiconductor, a dielectric, or a combination thereof(e.g., semiconductor on dielectric).

Illustratively, the substrate may include at least one selected fromsilicon, silicon oxide, aluminum oxide, magnesium oxide, siliconcarbide, silicon nitride, glass, quartz, sapphire, graphite, graphene,polyimide copolymer, polyimide, polyethylene naphthalate (PEN), afluoropolymer (FEP), and polyethylene terephthalate (PET). However, thematerial of the substrate is not limited thereto.

Next, the surface of the substrate is treated using a metal organicmaterial (120). Here, the process of treating the surface of thesubstrate includes: providing the metal organic material around thesubstrate; and heat-treating the vicinity of the substrate. Here, theheat-treating of the vicinity of the substrate may be performed at about500° C. or lower (for example, 300° C. to 500° C.).

Like this, when the metal organic material is provided around thesubstrate and the heat-treating of the vicinity of the substrate isperformed at 500° C. or lower, the metal organic material is decomposedto produce a metal, and this metal is formed on the surface of thesubstrate. The metal formed on the surface of the substrate in this waymay serve as a catalyst in the process of synthesizing transition metaldichalcogenide to be described later.

The metal organic material may include at least one selected from Al,Ti, and Ni. In this case, for example, the metal organic material mayinclude at least one selected from trimethylaluminum,tris(demethylamido)aluminum, triisobutylaluminum, titanium isopropoxide,tetrakis(dimethylamido)titanium, bis(cyclopentadienyl)nickel, andbis(ethylcyclopentadienyl)nickel. However, inventive concepts are notlimited thereto.

Subsequently, transition metal dichalcogenide is synthesized on thesurface of the substrate, and a transition metal dichalcogenide thinfilm is deposited (130). This thin film deposition process may beperformed at a temperature of about 500° C. (for example, 300° C. to500° C.).

The synthesis of the transition metal dichalcogenide may be performed onthe surface of the substrate by providing a transition metal precursorincluding a transition metal element and a chalcogen precursor includinga chalcogen element around the substrate. Here, the transition metalprecursor and the chalcogen precursor may be provided simultaneously oralternately to the substrate.

The transition metal precursor may include, for example, a transitionmetal halide. Here, for example, the transition metal halide includes atleast one selected from MoF₃, MoF₆, MoF₄, Mo₄F₂₀, MoCl₂, MoCl₃, MoCl₆,MoCl₄, MoCl₅, MoBr₃, MoBr₄, MoI₂, MoI₃, MoI₄, WF₆, WF₄, [WF₅]₄, WCl₂,WCl₆, WCl₄, [WCl₅]₂, [W₆Cl₁₂]Cl₆, WBr₃, WBr₆, WBr₄, WBr₅, W₆Br₁₄, WI₂,WI₃, WI₄, VF₂, VF₃, VF₄, VF₅, VCl₂, VCl₃, VCl₄, VBr₂, VBr₃, VBr₄, VI₂,VI₃, VI₄, NbCl₃, NbCl₄, NbCl₅, NbBr₄, NbBr₅, NbI₃, NbI₄, NbI₅, TaF₃,[TaF₅]₄, TaCl₃, TaCl₄, TaCl₅, TaBr₃, TaBr₄, TaBr₅, TaI₄, TaI₅, TiF₂,TiF₃, TiF₄, TiCl₄, TiCl₃, TiCl₂, TiBr₃, TiBr₄, HfCl₄, HfBr₂, HfBr₄,HfI₃, HfI₄, ZrF₄, ZrCl₂, ZrCl₃, ZrCl₄, ZrBr₃, ZrBr₄, ZrI₂, ZrI₃, ZrI₄,TcF₆, TcF₅, TcCl₄, TcCl₆, TcBr₄, ReF₆, ReF₄, ReF₅, ReF₇, Re₃Cl₉, ReCl₅,ReCl₄, ReCl₆, ReBr₃, ReBr₄, ReBr₅, ReI₃, ReI₄, CoF₂, CoF₃, CoF₄, CoCl₂,CoCl₃, CoBr₂, CoI₂, RhF₃, RhF₆, RhF₄, [RhF₅]₄, RhCl₃, RhBr₃, RhI₃, IrF₃,IrF₆, IrF₄, [IrF₅]₄, IrCl₂, IrCl₃, IrCl₄, IrBr₂, IrBr₃, IrBr₄, IrI₂,IrI₃, IrI₄, NiF₂, NiCl₂, NiBr₂, NiI₂, PdF₂, PdF₄, PdCl₂, PdBr₂, PdI₂,PtF₆, PtF₄, [PtF₅]₄, PtCl₂, PtCl₃, PtCl₄, Pt₆Cl₁₂, PtBr₂, PtBr₃, PtBr₄,PtI₂, PtI₃, PtI₄, GaF₃, GaCl₂, GaCl₃, GaBr₃, GaI₃, SnF₂, SnF₄, SnCl₂,SnCl₄, SnBr₂, SnBr₄, SnI₂, and SnI₄. However, inventive concepts are notlimited thereto.

The chalcogen precursor includes at least one selected from sulfur,hydrogen sulfide (H₂S), diethyl sulfide, dimethyl disulfide, ethylmethyl sulfide, (Et₃Si)₂S, selenium vapor, hydrogen selenide (H₂Se),diethyl selenide, dimethyl diselenide, ethyl methyl selenide,(Et₃Si)₂Se, selenium vapor, tellurium vapor, hydrogen telluride (H₂Te),dimethyl telluride, diethyl telluride, ethyl methyl telluride, and(Et₃Si)₂Te. However, inventive concepts are not limited thereto.

The metal organic material is decomposed by the surface treatment of thesubstrate to form a metal on the surface of the substrate, and thismetal induces the adsorption of the transition metal precursor and thechalcogen precursor on the substrate, thereby effectively synthesizingthe transition metal chalcogenide on the surface of the substrate.

Heretofore, there have been described a case where the surface treatmentof the substrate using the metal organic material is performed beforesynthesizing the transition metal dichalcogenide. However, inventiveconcepts are not limited thereto, and the surface treatment of thesubstrate using the metal organic material may also be performed whilesynthesizing the transition metal dichalcogenide.

The surface treatment of the substrate and the synthesis of thetransition metal dichalcogenide may be performed by an atomic layerdeposition (ALD) process or a chemical vapor deposition (CVD) process.However, inventive concepts are not limited thereto.

In general, the transition metal dichalcogenide is synthesized at hightemperatures of 600° C. or higher to form a thin film. Meanwhile, thereis a method of forming a thin film by synthesizing the transition metaldichalcogenide at low temperature of 600° C. or lower. However, in thiscase, in order to improve the quality of the thin film, the heattreatment is required to be performed at high temperatures of 600° C. orhigher. Further, in order to lower activation energy for synthesizingthe transition metal dichalcogenide, a method of forming a catalystmetal layer on a substrate or a method of treating the surface of asubstrate using H₂S has been used. However, the method of forming acatalyst metal layer on a substrate has a problem that a metal isadditionally deposited on the substrate through a separate process inorder to form the catalyst metal layer, and the method of treating thesurface of a substrate using H₂S has a problem that there is a substrate(for example, a silicon substrate) that is difficult to treat by H₂S.

According to the present embodiment, the surface of the substrate may betreated using the metal organic material at a relatively low temperatureof about 500° C. or lower, thereby effectively forming a high-qualitytransition metal dichalcogenide thin film on the surface of thesubstrate through one process (for example, an ALD process or a CVIDprocess).

FIG. 2 is a flowchart illustrating a method of forming a transitionmetal dichalcogenide thin film, according to another example embodiment.FIG. 2 illustrates a method of forming a transition metal dichalcogenidethin film using an ALD process.

Referring to FIG. 2 , first, a substrate is provided 210 in a processchamber that performs an ALD process (210). The substrate may, forexample, include a metal, a semiconductor, a dielectric, or acombination thereof (e.g., semiconductor on dielectric). As describedabove, the substrate may include at least one selected from silicon,silicon oxide, aluminum oxide, magnesium oxide, silicon carbide, siliconnitride, glass, quartz, sapphire, graphite, graphene, polyimidecopolymer, polyimide, polyethylene naphthalate (PEN), a fluoropolymer(FEP), and polyethylene terephthalate (PET). However, inventive conceptsare not limited thereto.

Next, the surface of the substrate is treated using a metal organicmaterial. Here, the metal organic material may include a metal forinducing the adsorption of a transition metal precursor and a chalcogenprecursor to be described later.

The metal organic material may include at least one selected from Al,Ti, and Ni. Specifically, for example, the metal organic material mayinclude at least one selected from trimethylaluminum,tris(demethylamido)aluminum, triisobutylaluminum, titanium isopropoxide,tetrakis(dimethylamido)titanium, bis(cyclopentadienyl)nickel, andbis(ethylcyclopentadienyl)nickel. However, inventive concepts are notlimited thereto.

The process of treating the surface of the substrate includes: providingthe metal organic material around the substrate (220); and heat-treatingthe vicinity of the substrate (230). Here, the heat-treating of thevicinity of the substrate may be performed at about 500° C. or lower(for example, 300° C. to 500° C.).

In the ALD process, the process of treating the surface of the substrateusing the metal organic material may be performed by repeatedlyproviding the metal organic material around the substrate at a desiredand/or alternatively predetermined heat treatment temperature in aplurality of cycles.

Specifically, first, the temperature in the process chamber ismaintained at a heat treatment temperature of 500° C. or lower (forexample, 300° C. to 500° C.) in a state in which the metal organicmaterial is supplied into the process chamber to provide the metalorganic material around the substrate. Accordingly, the metal organicmaterial supplied into the process chamber is decomposed to produce ametal, and the metal produced in this way is formed on the surface ofthe substrate. The metal formed on the surface of the substrate mayserve as a catalyst in the process of synthesizing transition metaldichalcogenide to be described later. That is, the metal formed on thesurface of the substrate may induce the adsorption of the transitionmetal precursor and the chalcogen precursor. The metal organic materialremaining in the process chamber after forming the metal on thesubstrate is discharged to the outside. Subsequently, a desired amountof metal may be formed on the surface of the substrate by repeatedlyperforming the aforementioned supply and discharge processes of themetal organic material in a plurality of cycles.

After the metal is formed on the surface of the substrate, transitionmetal dichalcogenide is synthesized on the surface of the substrateusing a general ALD process, thereby depositing a transition metaldichalcogenide thin film (240). Such a thin film deposition process maybe performed at a temperature of 500° C. or lower (for example, 300° C.to 500° C.).

Specifically, first, a transition metal precursor including a transitionmetal element is supplied into a process chamber. Here, the transitionmetal element may include at least one selected from Ti, Zr, Hf, V, Nb,Ta, Mo, W, Tc, Re, Co, Rh, Ir, N, Pd, Pt, Zn, and Sn. However, inventiveconcepts are not limited thereto.

The transition metal precursor may include a transition metal halide. Asdescribe above, the transition metal halide may include at least oneselected from MoF₃, MoF₆, MoF₄, Mo₄F₂₀, MoCl₂, MoCl₃, MoCl₆, MoCl₄,MoCl₅, MoBr₃, MoBr₄, MoI₂, MoI₃, MoI₄, WF₆, WF₄, [WF₅]₄, WCl₂, WCl₆,WCl₄, [WCl₅]₂, [W₆Cl₁₂]Cl₆, WBr₃, WBr₆, WBr₄, WBr₅, W₆Br₁₄, WI₂, WI₃,WI₄, VF₂, VF₃, VF₄, VF₅, VCl₂, VCl₃, VCl₄, VBr₂, VBr₃, VBr₄, VI₂, VI₃,VI₄, NbCl₃, NbCl₄, NbCl₅, NbBr₄, NbBr₅, NbI₃, NbI₄, NbI₅, TaF₃, [TaF₅]₄,TaCl₃, TaCl₄, TaCl₅, TaBr₃, TaBr₄, TaBr₅, TaI₄, TaI₅, TiF₂, TiF₃, TiF₄,TiCl₄, TiCl₃, TiCl₂, TiBr₃, TiBr₄, HfCl₄, HfBr₂, HfBr₄, HfI₃, HfI₄,ZrF₄, ZrCl₂, ZrCl₃, ZrCl₄, ZrBr₃, ZrBr₄, ZrI₂, ZrI₃, ZrI₄, TcF₆, TcF₅,TcCl₄, TcCl₆, TcBr₄, ReF₆, ReF₄, ReF₅, ReF₇, Re₃Cl₉, ReCl₅, ReCl₄,ReCl₆, ReBr₃, ReBr₄, ReBr₅, ReI₃, ReI₄, CoF₂, CoF₃, CoF₄, CoCl₂, CoCl₃,CoBr₂, CoI₂, RhF₃, RhF₆, RhF₄, [RhF₅]₄, RhCl₃, RhBr₃, RhI₃, IrF₃, IrF₆,IrF₄, [IrF₅]₄, IrCl₂, IrCl₃, IrCl₄, IrBr₂, IrBr₃, IrBr₄, IrI₂, IrI₃,IrI₄, NiF₂, NiCl₂, NiBr₂, NiI₂, PdF₂, PdF₄, PdCl₂, PdBr₂, PdI₂, PtF₆,PtF₄, [PtF₅]₄, PtCl₂, PtCl₃, PtCl₄, Pt₆Cl₁₂, PtBr₂, PtBr₃, PtBr₄, PtI₂,PtI₃, PtI₄, GaF₃, GaCl₂, GaCl₃, GaBr₃, GaI₃, SnF₂, SnF₄, SnCl₂, SnCl₄,SnBr₂, SnBr₄, SnI₂, and SnI₄.

Next, a chalcogen precursor including a chalcogen element is suppliedinto the process chamber. Here, the chalcogen element may include atleast one selected from S, Se, and Te. However, inventive concepts arenot limited thereto.

As described above, the chalcogen precursor may include at least oneselected from sulfur, hydrogen sulfide (H₂S), diethyl sulfide, dimethyldisulfide, ethyl methyl sulfide, (Et₃Si)₂S, selenium vapor, hydrogenselenide (H₂Se), diethyl selenide, dimethyl diselenide, ethyl methylselenide, (Et₃Si)₂Se, selenium vapor, tellurium vapor, hydrogentelluride (H₂Te), dimethyl telluride, diethyl telluride, ethyl methyltelluride, and (Et₃Si)₂Te.

When the temperature in the process chamber is maintained at atemperature of about 500° C. or lower, for example, 300° C. to 500° C.,the transition metal precursor reacts with the chalcogen precursor onthe surface of the substrate to synthesize the transition metaldichalcogenide.

As described above, since the metal is formed on the surface of thesubstrate using the metal organic material through the heat treatmentprocess, the transition metal precursor and the chalcogen precursor maybe effectively adsorbed on the surface of the substrate, and thus thetransition metal dichalcogenide may be easily synthesized. Then, thetransition metal precursor and the chalcogen precursor remaining in theprocess chamber are discharged to the outside. Subsequently, atransition metal dichalcogenide thin film having a desired thickness isdeposited on the surface of the substrate by repeatedly performing theaforementioned supply and discharge processes of the transition metalprecursor and the chalcogen precursor in a plurality of cycles.

As described above, according to the present embodiment, the surface ofthe substrate is treated at a temperature of about 500° C. or lowerusing the metal organic material through the ALD process, and then thetransition metal dichalcogenide is synthesized on the surface of thesubstrate, thereby effectively forming a high-quality transition metaldichalcogenide thin film on the surface of the substrate.

Heretofore, there have been described a case where the surface treatmentof the substrate using the metal organic material is performed beforesynthesizing the transition metal dichalcogenide through the ALDprocess. However, inventive concepts are not limited thereto, and thesurface treatment of the substrate using the metal organic material mayalso be performed while synthesizing the transition metal dichalcogenidethrough the ALD process.

FIGS. 3A and 3B are a Raman spectrum and a PL spectrum illustrating acase where an MoS₂ thin film is deposited on an SiO₂ substrate using anALD process without surface-treating the SiO₂ substrate usingtrimethylaluminum (TMA).

In FIGS. 3A and 3B, in the deposition process of a MoS₂ thin film, MoCl₅was used as a transition metal precursor, and H₂S was used as achalcogen precursor. Further, a chamber coated with SiO₂ was used as adeposition apparatus, and a canister for supplying a MoCl₅ precursor wasmaintained at a temperature of 160° C. Further, the supply time andpurging time of MoCl₅ at 420° C. was 2 seconds and 10 seconds as 1cycle, respectively, and the supply time and purging time of H₂S at 420°C. was 20 seconds and 10 seconds as 1 cycle, respectively. The supplyand purging of MoCl₅ and the supply and purging of H₂S were performedfor total 400 cycles, respectively.

Referring to FIGS. 3A and 3B, it may be found that almost no transitionmetal chalcogenide thin film was formed on the surface of a SiO₂substrate when the surface of the SiO₂ substrate was not treated usingtrimethylaluminum (TMA).

FIGS. 4A and 4B are a Raman spectrum and a PL spectrum illustrating acase where an MoS₂ thin film was deposited after surface-treating a SiO₂substrate for 20 cycles using trimethylaluminum (TMA) through an ALDprocess.

Referring to FIGS. 4A and 4B, in the surface treatment process usingTMA, the supply time and purging time of TMA at 420° C. was 1 second and20 seconds as 1 cycle, respectively. The supply and purging of TMA wereperformed for total 20 cycles. In the deposition process of a MoS₂ thinfilm, MoCl₅ was used as a transition metal precursor and H₂S was used asa chalcogen precursor. Further, a chamber coated with SiO₂ was used as adeposition apparatus, and a canister for supplying a MoCl₅ precursor wasmaintained at a temperature of 160° C. Further, the supply time andpurging time of MoCl₅ at 420° C. was 2 seconds and 10 seconds as 1cycle, respectively, and the supply time and purging time of H₂S at 420°C. was 20 seconds and 10 seconds as 1 cycle, respectively. The supplyand purging of MoCl₅ and the supply and purging of H₂S were performedfor total 400 cycles, respectively.

Referring to FIGS. 4A and 4B, it may be found that a transition metalchalcogenide thin film having monolayer characteristics was formed onthe surface of a SiO₂ substrate when the surface of the SiO₂ substratewas treated using TMA for 20 cycles.

FIGS. 5A and 5B are a Raman spectrum and a PL spectrum illustrating acase where a MoS₂ thin film was deposited through an ALD process aftersurface-treating a SiO₂ substrate for 50 cycles using trimethylaluminum(TMA) through the ALD process.

Referring to FIGS. 5A and 5B, in the surface treatment process usingTMA, the supply time and purging time of TMA at 420° C. was 1 second and20 seconds as 1 cycle, respectively. The supply and purging of TMA wereperformed for total 50 cycles. In the deposition process of a MoS₂ thinfilm, MoCl₅ was used as a transition metal precursor, and H₂S was usedas a chalcogen precursor. Further, a chamber coated with SiO₂ was usedas a deposition apparatus, and a canister for supplying a MoCl₅precursor was maintained at a temperature of 160° C. Further, the supplytime and purging time of MoCl₅ at 420° C. was 2 seconds and 10 secondsas 1 cycle, respectively, and the supply time and purging time of H₂S at420° C. was 20 seconds and 10 seconds as 1 cycle, respectively. Thesupply and purging of MoCl₅ and the supply and purging of H₂S wereperformed for total 400 cycles, respectively.

Referring to FIGS. 5A and 5B, it may be found that a transition metalchalcogenide thin film having monolayer characteristics was formed onthe surface of a SiO₂ substrate when the surface of the SiO₂ substratewas treated using TMA for 50 cycles. Further, it may found that, whenthe surface treatment using TMA was performed for 50 cycles, ahigh-quality transition metal dichalcogenide thin film was formedcompared to when the surface treatment using TMA was performed for 20cycles.

FIG. 6 is a flowchart illustrating a method of forming a transitionmetal dichalcogenide thin film, according to another example embodiment.FIG. 6 illustrates a method of forming a transition metal dichalcogenidethin film using a CVD process.

Referring to FIG. 6 , first, a substrate is provided 310 in a processchamber that performs an ALD process (310). The substrate may, forexample, include a metal, a semiconductor, a dielectric, or acombination thereof (e.g., semiconductor on dielectric).

Next, the surface of the substrate is treated using a metal organicmaterial. Here, the metal organic material may include a metal forinducing the adsorption of a transition metal precursor and a chalcogenprecursor to be described later.

The metal organic material may include at least one selected from Al,Ti, and Ni. Specifically, for example, the metal organic material mayinclude at least one selected from trimethylaluminum,tris(demethylamido)aluminum, triisobutylaluminum, titanium isopropoxide,tetrakis(dimethylamido)titanium, bis(cyclopentadienyl)nickel, andbis(ethylcyclopentadienyl)nickel. However, inventive concepts are notlimited thereto.

The process of treating the surface of the substrate includes: providingthe metal organic material around the substrate (320); and heat-treatingthe vicinity of the substrate (330). Here, the heat-treating of thevicinity of the substrate may be performed at about 500° C. or lower(for example, 300° C. to 500° C.).

Specifically, the temperature in the process chamber is maintained at aheat treatment temperature of 500° C. or lower (for example, 300° C. to500° C.) in a state in which the metal organic material is supplied intothe process chamber to provide the metal organic material around thesubstrate. Accordingly, the metal organic material supplied into theprocess chamber is decomposed to produce a metal, and the metal producedin this way is formed on the surface of the substrate. Here, the metalformed on the surface of the substrate may induce the adsorption of thetransition metal precursor and the chalcogen precursor. The metalorganic material remaining in the process chamber after forming themetal on the substrate is discharged to the outside.

After the metal is formed on the surface of the substrate, transitionmetal dichalcogenide is synthesized on the surface of the substrateusing a general CVD process, thereby depositing a transition metaldichalcogenide thin film (340). Such a thin film deposition process maybe performed at a temperature of 500° C. or lower (for example, 300° C.to 500° C.).

Specifically, a transition metal precursor including a transition metalelement is supplied into a process chamber. Here, the transition metalelement may include at least one selected from Ti, Zr, Hf, V, Nb, Ta,Mo, W, Tc, Re, Co, Rh, Ir, N, Pd, Pt, Zn, and Sn. The transition metalprecursor may include a transition metal halide. The chalcogen elementmay include at least one selected from S, Se, and Te. However, inventiveconcepts are not limited thereto.

When the temperature in the process chamber is maintained at atemperature of about 500° C. or lower, for example, 300° C. C to 500° C.C, the transition metal precursor reacts with the chalcogen precursor onthe surface of the substrate to synthesize the transition metaldichalcogenide.

As described above, since the metal is formed on the surface of thesubstrate using the metal organic material through the heat treatmentprocess, the transition metal precursor and the chalcogen precursor maybe effectively adsorbed on the surface of the substrate, and thus thetransition metal dichalcogenide may be easily synthesized. Accordingly,a transition metal dichalcogenide thin film having a desired thicknessmay be deposed on the surface of the substrate

As described above, according to the present embodiment, the surface ofthe substrate is treated at a temperature of about 500° C. using themetal organic material through the CVD process, and then the transitionmetal dichalcogenide is synthesized on the surface of the substrate,thereby effectively forming a high-quality transition metaldichalcogenide thin film on the surface of the substrate.

Heretofore, there have been described a case where the surface treatmentof the substrate using the metal organic material is performed beforesynthesizing the transition metal dichalcogenide through the CVDprocess. However, inventive concepts are not limited thereto, and thesurface treatment of the substrate using the metal organic material mayalso be performed while synthesizing the transition metal dichalcogenidethrough an ALD process.

According to the aforementioned embodiment, the surface of the substratemay be treated using the metal organic material at a relatively lowtemperature of about 500° C. or lower, thereby effectively forming ahigh-quality transition metal dichalcogenide thin film on the surface ofthe substrate through one process (for example, an ALD process or a CVDprocess.

It should be understood that embodiments described herein should beconsidered in a descriptive sense only and not for purposes oflimitation. Descriptions of features or aspects within each embodimentshould typically be considered as available for other similar featuresor aspects in other embodiments. While one or more embodiments have beendescribed with reference to the figures, it will be understood by thoseof ordinary skill in the art that various changes in form and detailsmay be made therein without departing from the spirit and scope asdefined by the following claims.

What is claimed is:
 1. A method of forming a transition metaldichalcogenide thin film on a substrate, the method comprising: treatingthe substrate with a metal organic material, the metal organic materialincluding a metal; and providing a transition metal precursor and achalcogen precursor around the substrate to synthesize a transitionmetal dichalcogenide on the substrate, the transition metal precursorincluding a transition metal element and the chalcogen precursorincluding a chalcogen element, wherein the treating the substrateprovides the metal on a surface of the substrate, the treating thesubstrate is performed without using H₂S and includes heat-treating avicinity of the substrate at a process temperature of 300° C. to 500° C.to decompose the metal organic material.
 2. The method of claim 1,wherein the metal on the surface of the substrate induces adsorption ofthe transition metal precursor and the chalcogen precursor onto thesubstrate.
 3. The method of claim 1, wherein the metal of metal organicmaterial includes at least one of Al, Ti, and Ni.
 4. The method of claim3, wherein the metal organic material includes at least one oftrimethylaluminum, tris(demethylamido)aluminum, triisobutylaluminum,titanium isopropoxide, tetrakis(dimethylamido)titanium,bis(cyclopentadienyl)nickel, and bis(ethylcyclopentadienyl)nickel. 5.The method of claim 1, wherein the transition metal dichalcogenide isrepresented by Formula 1 below:M_(1-a)M_(a)′X_(2(1-b))X_(2b)′  <Formula 1> wherein, in Formula 1, M andM′ are different transition metal elements from each other, X and X′ aredifferent chalcogen elements from each other, 0≤a<1, and 0≤b<1.
 6. Themethod of claim 1, wherein the transition metal element includes atleast one of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Tc, Re, Co, Rh, Ir, Ni, Pd,Pt, Zn, and Sn, and the chalcogen element includes at least one of S,Se, and Te.
 7. The method of claim 1, wherein the transition metalprecursor includes a transition metal halide.
 8. The method of claim 7,wherein the transition metal halide includes at least one of MoF₃, MoF₆,MoF₄, Mo₄F₂₀, MoCl₂, MoCl₃, MoCl₆, MoCl₄, MoCl₅, MoBr₃, MoBr₄, MoI₂,MoI₃, MoI₄, WF₆, WF₄, [WF₅]₄, WCl₂, WCl₆, WCl₄, [WCl₅]₂, [W₆Cl₁₂]Cl₆,WBr₃, WBr₆, WBr₄, WBr₅, W₆Br₁₄, WI₂, WI₃, WI₄, VF₂, VF₃, VF₄, VF₅, VCl₂,VCl₃, VCl₄, VBr₂, VBr₃, VBr₄, VI₂, VI₃, VI₄, NbCl₃, NbCl₄, NbCl₅, NbBr₄,NbBr₅, NbI₃, NbI₄, NbI₅, TaF₃, [TaF₅]₄, TaCl₃, TaCl₄, TaCl₅, TaBr₃,TaBr₄, TaBr₅, TaI₄, TaI₅, TiF₂, TiF₃, TiF₄, TiCl₄, TiCl₃, TiCl₂, TiBr₃,TiBr₄, HfCl₄, HfBr₂, HfBr₄, HfI₃, HfI₄, ZrF₄, ZrCl₂, ZrCl₃, ZrCl₄,ZrBr₃, ZrBr₄, ZrI₂, ZrI₃, ZrI₄, TcF₆, TcF₅, TcCl₄, TcCl₆, TcBr₄, ReF₆,ReF₄, ReF₅, ReF₇, Re₃Cl₉, ReCl₅, ReCl₄, ReCl₆, ReBr₃, ReBr₄, ReBr₅,ReI₃, ReI₄, CoF₂, CoF₃, CoF₄, CoCl₂, CoCl₃, CoBr₂, CoI₂, RhF₃, RhF₆,RhF₄, [RhF₅]₄, RhCl₃, RhBr₃, RhI₃, IrF₃, IrF₆, IrF₄, [IrF₅]₄, IrCl₂,IrCl₃, IrCl₄, IrBr₂, IrBr₃, IrBr₄, IrI₂, IrI₃, IrI₄, NiF₂, NiCl₂, NiBr₂,NiI₂, PdF₂, PdF₄, PdCl₂, PdBr₂, PdI₂, PtF₆, PtF₄, [PtF₅]₄, PtCl₂, PtCl₃,PtCl₄, Pt₆Cl₁₂, PtBr₂, PtBr₃, PtBr₄, PtI₂, PtI₃, PtI₄, GaF₃, GaCl₂,GaCl₃, GaBr₃, GaI₃, SnF₂, SnF₄, SnCl₂, SnCl₄, SnBr₂, SnBr₄, SnI₂, andSnI₄.
 9. The method of claim 1, wherein the chalcogen precursor includesat least one of sulfur, hydrogen sulfide (H₂S), diethyl sulfide,dimethyl disulfide, ethyl methyl sulfide, (Et₃Si)₂S, selenium vapor,hydrogen selenide (H₂Se), diethyl selenide, dimethyl diselenide, ethylmethyl selenide, (Et₃Si)₂Se, selenium vapor, tellurium vapor, hydrogentelluride (H₂Te), dimethyl telluride, diethyl telluride, ethyl methyltelluride, and (Et₃Si)₂Te.
 10. The method of claim 1, wherein thesubstrate includes at least one of silicon, silicon oxide, aluminumoxide, magnesium oxide, silicon carbide, silicon nitride, glass, quartz,sapphire, graphite, graphene, polyimide copolymer, polyimide,polyethylene naphthalate (PEN), a fluoropolymer (FEP), and polyethyleneterephthalate (PET).
 11. The method of claim 1, wherein the treating thesubstrate with the metal organic material includes providing the metalorganic material around the substrate.
 12. The method of claim 11,wherein the heat-treating the vicinity of the substrate provides themetal on the surface of the substrate by the decomposition of the metalorganic material on the substrate.
 13. The method of claim 1, whereinthe providing the transition metal precursor and the chalcogen precursoraround the substrate forms the transition metal dichalcogenide thin filmby an atomic layer deposition (ALD) process or a chemical vapordeposition (CVD) process.
 14. The method of claim 1, wherein thetreating the substrate with the metal organic material is performedbefore the providing the transition metal precursor and the chalcogenprecursor around the substrate to synthesize the transition metaldichalcogenide or during the providing the transition metal precursorand the chalcogen precursor around the substrate to synthesize thetransition metal dichalcogenide.
 15. The method of claim 1, wherein thetransition metal precursor and the chalcogen precursor are providedsimultaneously to the substrate or provided alternately to thesubstrate.
 16. A method of forming a transition metal dichalcogenidethin film on a substrate, the method comprising: treating the substratewith a metal organic material, the metal organic material including ametal; and synthesizing a transition metal dichalcogenide on thesubstrate using an atomic layer deposition (ALD) process, wherein thetreating the substrate provides the metal on a surface of the substrate,and the treating the substrate is performed without using H₂S andincludes heat-treating a vicinity of the substrate at a processtemperature of 300° C. to 500° C. to decompose the metal organicmaterial.
 17. The method of claim 16, wherein the forming of thetransition metal dichalcogenide thin film is performed at 300° C. to500° C.
 18. A method of forming a transition metal dichalcogenide thinfilm on a substrate, the method comprising: treating the substrate witha metal organic material, the metal organic material including a metal;and synthesizing a transition metal dichalcogenide on the substrateusing a chemical vapor deposition (CVD) process, wherein the treatingthe substrate provides the metal on a surface of the substrate, and thetreating the substrate is performed without using H₂S and includesheat-treating a vicinity of the substrate at a process temperature of300° C. to 500° C. to decompose the metal organic material.
 19. Themethod of claim 18, wherein the forming of the transition metaldichalcogenide thin film is performed at 300° C. to 500° C.